Method of preparing aqueous dispersions of synthetic resins



Patented Apr. 29, 1947 METHOD OF PREPARING AQUEOUS DIS- PERSIONS OF SYNTHETIC BESINS Charles F. Brown, Middiebnry, Com, assignor, by mesne assignments, to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing.

Claims.

This invention relatesto a method of preparing aqueous dispersions of certain synthetic resins, more particularly aqueous dispersions of certain synthetic resins on soaps as the dispersing agents.

Natural rubber, as is known, may readily be dispersed in water by milling or otherwise plasticizing the rubber, incorporating a hydrophilic colloidal dispersing agent, for example soap, solubilized casein, or colloidal clay, and adding water while stretching and kneading the plasticized mass, as in an internal mixer, such as Werner 8: Pfleiderer type mixer, until an inversion of phase takes place, and the rubber becomes dispersed in the aqueous medium. Gums, bitumens, and cellulose esters have been similarly dispersed in water. Many synthetic resins, even after the addition of conventional plasticizing agents, cannot be dispersed in water with soap as the dispersing agent because such synthetic resins are resistant to and will not absorb soap-forming acids or soaps in such a manner that the addition of water thereto, as in an internal mixer, will cause an inversion of phase and dispersion of the synthetic resin in the aqueous medium. In these cases, the synthetic resin containing the soap breaks up in small pieces on addition of the water and the soap merely exudes to the surface oi the pieces of synthetic resin.

By the present invention, aqueous dispersions of certain synthetic resins may readily be prepared with soaps as the dispersing agents.

In carrying out my invention, the heat-reaction product of rosin, an alkanolamine, a glycol, and a dimerized acid of a vegetable drying oil is mixed with the synthetic resin before dispersing the resin on the soap. This reaction product acts to improve the receptiveness of the synthetic resin to soap, whereby after the soap is milled in, water may be added as in an internal mixer until inversion of phase readily takes place and the synthetic resin becomes dispersed, together with the added heat-reaction product, in-the aqueous medium containing the soap. The heat-reaction product of rosin, an alkanolamine, a glycol, and a dimerized acid or a vegetable drying oil, and the method of preparing the same, is disclosed in my copending application Serial No. 507,295,

7 filed October 22, 1943. As disclosed in that case,

the glycol and dimerized acid of a vegetable dry- Application October 20, 1944, Serial No. 559,651

ing oil may first be reacted to form a so-called polyester which itself is a known commercial synthetic resin, sold under the trade names Norepol and Asripol, The polyester, or the glycol and dimerized acid of a vegetable drying oil, is reacted at elevated temperatures with rosin and an alkanolamine to form the heat-reaction product which is used in the present invention to' aid in dispersing certain dillicultly dispersible synthetic resins in water. Examples of the preparation of the heat-reaction product, accordingto my prior patent application Serial No, 507,295, are given below.

The heat-reaction product may be produced by heating for about 5 to 15 hours at a temperature from about 180 C. to 300 C., a mix containing rosin, an alkanolamine, a glycol and a dimerized acid of a vegetable drying oil, or an equivalent mix containing rosin, an alkanolamine and a polyester. The alkanolamine may be a monoor dior tri-substituted alkanolamine, or a mixture thereof, e. g., monoethanolamine, diethanolamine, triethanolamine, although the tri-substi-' tuted alkanolamines are preferred. The term polyester? refers to the synthetic resin obtained by reacting a glycol with a dimerized acid of a vegetable drying oil, such as soy bean oil, tung oil, linseed oil, or other unsaturated vegetable oil acid. By dimerized i meant the combination of two molecules of the unsaturated acid by addition polymerization. These are the conventional meanings of the terms.

The reactions taking place between the components present are varied and complex. The polyester when added as such probably breaks down into its several reacting groups, which groups or bodies react with other bodies present to give various products differing from the original reactants. The dimerized acid and glycol, when added separately, either provide such reactive groups, or may react to give a polyester,

which in turn may give up reactive bodies as postulated. The dimerized acid and glycol, when added separately, should be added to a weight equivalent to the weight of the polyester. For

example, 87.5 parts of dimerized acids of soy bean oil, and 12.5 partsof ethylene glycol, are equivalent to parts of the corresponding polyester. In some cases, an excess of the glycol may be used beyond that entering into combination. As such, the glycol seems to act as a plasticizer and does not materially change the basic heat-reaction product or resin formed. The proportion of the reactants may be varied over a wide range and they may be admixed with other materials before, during, or after the reaction; for example, a polyvinyl acetal resin may be additionally added. Proportions, by weight, are exemplified by the following:

Parts Rosin 25-100 Triethanolamine 25-100 Polyester 50-200 Example I Parts Rosin 100 Triethanolamine 100 Polyester 100 The polyester" and that of Example II is a combination prepared from a dimerized acid derived from such as soy bean oil, said dimerized acid being reacted with ethylene glycol and the reaction product containing about 12 /2% ethylene glycol. It is sold under the trade name Norepol.

The rosin and the amine are mixed and heated to about 180 C. until the ingredients form a homogeneous solution. Then the polyester is added and the reaction mixture is heated together in a suitable container at 200-230" C. for about 9 or 10 hours, or until incipient gelling takes place. At the indication of gelling, the mix- The dimerized acid and that of Example IV corresponds to the dimerized unsaturated long chain fatty acid or acids such as those derived from soy bean oil. gether as in Example I and the heat-reaction product has characteristics equivalent to that of Example I.

Example IV A heat-reaction product corresponding to that produced in Example 11 is obtained from:

I Parts Rosin 100 Triethanolamine -1 100 Dimerized acids 74.4 Ethylene glycol 10.6 Polyvinyl butyral resin 15 The reactants are heated together as in Example II, and the products obtained are substantially identical in characteristics with those fro Example II.

Products such as the above and illustrated in previous Examples I to IV, will be termed heatreaction products of rosin, an alkanol amine, a glycol and a dimerized acid of a vegetable drying oil, or a dimerized unsaturated acid of a vegetable oil. Such resinous heat-reaction products may readily be milled into synthetic resins. With ture is dumped from the reaction vessel and allowed to cool. The product is a dark, very sticky, adhesive, gel-like resin that is insoluble in all of the common solvents, except the benzenpid and chlorinated hydrocarbons.

Example 11 The reactionproduct may be further modified by the incorporation of other resins. These resins serve to add strength to the composition and do not materially change the properties of the basic heat-reaction product. A preferred mixture is:

' Parts Rosin 100 Triethanolamine 100 Polyester 85 Polyvinyl butyral resin 15 The reaction mixture is heated as in Example I. The product has characteristics substantially identical with that cited in Example I except that the composition is stifier and stronger.

Example III It is not always necessary that the polyester be added as such. The ingredients may be added certain synthetic resins, the heat-reaction product will permit the admixture of soaps with the synthetic resin mass and give an inversion of phase on addition of water with dispersing of the synthetic resin and added heat-reaction product in the aqueous medium. The amount of the heatreaction product added to the synthetic resin is not critical, additions of from 5 to 50 parts of the heat-reaction product of the above examples per parts of synthetic resin effectively aiding the dispersing of the synthetic resin in water. In

general, increased amounts of the heat-reaction product give increased viscos'ities, and increased tack to films laid down from the dispersions.

Synthetic resins which have been dispersed in water on soap as the dispersing agent with the aid of the above heat-reaction products are polymers of butadienes-l,3, copolymers of butadie'nes-1,3 with other polymerizable compounds, polyisobutylene, copolymers of isobutylene and a small amount of a conjugated diene, organic polysulfide polymers, polyvinylchloride, copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers. It may be necessary or advisable in many cases to incorporate conventional plasticizers in the synthetic resin before dispersing. The applicant has not succeeded in dispersing polyvinyl acetate or polystyrene on soap by the method of the present invention.

Illustrative of polymers of butadienes-IB are the polymers of butadiene-1,3, methyI-Z-butadime-1,3 (isoprene), ch1or0-2 butadiene 1,3 (chloroprene); piperylene, and 2,3-dirnethylbutadiene-1,3. .Illustrative of the copolyir'iers of butadienes-1,3 with other polymeriaable compounds which are capable of formingbo'polymers The reactants are heated tothe alpha-methylene carboxylic acids, and their esters, nitriles and amides, such as acrylic acid, methyl acrylate, methyl methacrylate, acryloniwater. Further water was added to trile, methacrylonitrile, methacrylamlde; methyl vinyl ether; methyl vinyl ketone; vinylidene chloride. Examples of commercial synthetic rubbers which are polymers of copolymers of butadienes- 1,3 as above are neoprene r GRM rubber (polymerized chloro-2-butadiene-1,3), Buna S or GRS rubber (copolymer of butadiene-1,3 and styrene), and Buna N or GRN rubber (copolymer of butadiene and a'crylonitrile) Polyisobutylene is commercially known as Vistanex. Illustrative of copolymers of isobutylene with a small amount of a conjugateddiene, are copolymers of isobutylene with l to of butadiene-1,3 or methyl-Z-butadiene-1,3 (isoprene) These are known as Butyl or GRI rubbers. Illustrative of synthetic rubbers which are organic polysulphide polymers are the commercial "Thioko which are substantial- 1y polymers of the structural unit or the structural unit +-Snn] where preparation of aqueous dispersions oi various synthetic resins according to the present invention utilizing the heat-reaction products of prior Examples Ito IV as dispersing aids for the synthetic resins prior to dispersing on soap. In some cases the heat-reaction product itself sumciently plasticizes the synthetic resin before dispersion, whereas in other cases, the synthetic resin should 7 phase.

whereupon the neoprene became dispersed in the the desired concentration of 60% solids.

Compounding and modifying ingredients, such as other resins, fillers, curatives, pigments, loadins materials and the like, maybe added to the plasticized mix on the mill or in the Werner 8: Pileiderer mixer prior to addition of water to inversion of phase, as in the case of dispersion of natural rubber. I

Eaample VI 100 parts of commercial Buna S rubber (co-.

polymer of butadiene and styrene) were mixed on a mill with 15 parts of the heat-reaction product of Example II. This batch was placed in a Werner 8: Pfleiderer mixer and 8 parts of stearic acid were added together with a.- small amount of water followed by 2 p a"ts of potassium hydroxide dissolved in a small amount of water to form the soap. Water was then added to inversion of Example VII 100 parts of commercial Buns. N (copolymer of butadiene and .acrylonitrile) were mixed on a mill with 25 parts of the heat-reaction product was transferred to a Werner 8: Pfleiderer mixer where 1.3 parts of sodium hydroxide dissolved in a small amount of water were mixed in. Water was then slowly added with continuous kneading and stretching of the mass in the mixer until an inversion of phase took place and the 'Buna N rubber became dispersed in the aqueous medium.

Example VIII soap in situ. Water was then added slowly to additionally be plasticized with a conventional plasticizer for the synthetic resin in a known manner, before dispersing the synthetic resin.

The soap may be added as such or formed in-situ in the synthetic resin mass. The soap may be a conventional soap dispersing agent, such as an alkali-metal, ammofiium, alkylamine, alkanolamine, or morpholine soap; All parts in the following examples are by weight.

Erample V the total addition of about25 parts of water,

inversion of phase.

Example IX parts of commercial Butyl rubber (copolymer of isobutylene with about 1 to 2% isoprene) were mixed on a mill with 20 parts of the heatreaction product of Example III. The plasticized mass was transferred to a Werner 8; Pfleiderer mixed where 6 parts of stearic acid were added with continuous mixing together with a small amount of water followed by 1.3 parts of sodium hydroxide dissolved in a small amount of water to form the sodium soap. Water was then added with continuous kneading and stretching of the mass in themixer in the usual manner until inversion of phase took place and a stable aqueous dispersion was obtained.

Example X product of Example II. 6 parts of oleic acid and a small amount of water were added to the Thiokol batch.- The mass was then transferred to a geneous. To

1 Werner 8: Pfleiderer mixer where 1.8 parts of sodium hydroxide dissolved in a small amount of water were added to form the soap, after which water was slowly added with continuous stretching and kneading in the mixer until an inversion of phase took place.

Example XI 100 parts of polyvinyl chloride were placed in 9. Werner & Pileiderer type mixer. There was added 100 parts oi dibutoxyethylphthalate, a con-,- ventional plasticizer, and 15 parts of the heat-reaction product of Example II. The batch was plasticized in the mixer until the mass was homothe plasticized batch was added 8 parts of oleic acid which was. well worked into the mix. 2.5 parts of potassium hydroxide dis-- solved in a small amount of water were added to form the soap, after which water was slowly added with continuous stretching and kneading until inversion in phase took place and the desired concentration between 50 and 60% solids was obtained.

Example XII Example XIII Butyl methacrylate polymer and butyl-isobutyl methacrylate polymer were each dispersed in the same manner as the polyvinyl chloride in Example XI.

Example XIV This case illustrates the dispersing of a mixture of synthetic resins according to the present invention. 3

100 parts of polyvinyl chloride were placed in an internal mixer of the Werner & Pfleiderer type, and 100 parts of dibutyl phthalate plasticizer were added. 30 parts of acoplymer of hutadiene-1,3 and acrylonitrile (commercial Hycar OR-l5) and 15 parts of the heat-reaction prodnot of Example 11 was added, and the batch was plasticized in the mixer until the mass was homogeneous. To the batch was then added 5 parts of oleic acid which was well worked into the mix followed by 2 parts of potassium hydroxide dissolved in a small amount of waten. Water was then added slowly until inversion in phase took place followed by additional water to the desired concentration of 50-60% solids.

Examples 'V to XIV disclose the dispersion of various synthetic resins according to the present invention using soap as the dispersing agent, soap dispersions being the most diflicult dispersions of synthetic resins to prepare due to the resistance of the synthetic resins to the softening effects of soap-forming acids and soaps. However, the heat reaction products such as shown in Examples I to IV, will effectively aid in the dispersing of the synthetic resins on other dispersing agents than soaps, such as proteins, for example solubilized casein, or colloidal clay.

In view of the many changes and modifications Having thus described my invention, what I claim and desire to protect by Letters Patent is:

l. The method or preparing an aqueous dispersion of synthetic resin selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, which comprises mixing with such synthetic resin aplasticizer therefor, a heat-reaction product, at a temperature in the range of between about C. and 300 C., of a mix containing rosin, an alkanolamlne, an alblene glycol and a dimerized acid of a vegetable drying oil, and also mixing with the synthetic resin a hydrophilic colloidal dispersing agentselected fromthe group consisting of soaps, proteins, solubilized casein and colloidal clay, and iailding water until an inversion of phase takes p ace.

2. The method of preparing an aqueous dispersion of synthetic resin selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, which comprises mixing with such synthetic resin a plasticizer therefor,

' a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and a dimerized acid of a vegetable drying oil, and also mixing with the synthetic resin a soap, and adding water until an inversion of phase takes place.

3. The method of preparing an aqueous dispersion of synthetic resin' selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkylmethacrylate polymers, which comprises mixing with such synthetic resin a plasticizer therefor,

a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and dimerized acid of soy bean oil,and also mixing with the synthetic resin a hydrophilic colloidal dipersing agent selected from the group consisting of soaps, proteins, solubilized casein andcolloidal clay, and adding water until an inversion of phase takes place.

4. The method of preparing an aqueous dispersion of synthetic resin selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, which comprises mixing with such synthetic resin a plasticizer therefor, a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an alkylene glycol and dimerized acid of soy bean oil, and also mixing with the synthetic resin a soap, and adding water until an inversion of phase takes place.

5. The method of preparing an aqueous dispersion of an alkyl methacrylate polymer which comprises mixing with said polymer a plasticizer therefor, a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an alkylene glycol and a dimerized acid of a vegetable drying oil, and also mixing with said polymer a hydrophilic colloidal dispersing agent selected from the group consisting of soaps, proteins, solubilized casein and colloidal clay, and

adding water until an inversion of phase takes place.

6. The method of preparing an aqueous dispersion of an alkyl methacrylate polymer which comprises mixing with said polymer a plasticizer therefor, a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., ofa mix containing rosin, analkanob' amine, ethylene glycol and dimerized acid of soy bean oil, and also mixing with said polymer a soap, and adding water until an inversion oi phase takes place.

7. The method of preparing an aqueous dis-,

persion of polyvinyl chloride which comprises mixing with said polyvinyl chloride a plasticizer therefor, a heat-reaction product, at a temperature in the range or between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an alkylene glycol and a dimerized acid of a vegetable drying oil, and also mixing with said polyvinyl chloride a hydrophillc colloidal dispersing agent selected from the group consisting of soaps, proteins, solubilized casein and colloidal clay. and adding water until an inversion of phase takes place.

8. The method of preparing an aqueous dis-\ acetate which comprises mixing with said copolymer a plasticizer therefor, a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an alkylene glycol and a dimerized acid of a vegetable drying oil, and also mixing with said copolymer a hydrophilic colloidal dispersing agent selected from the group consisting of soaps, proteins, solubilized casein and colloidal clay, and adding water until an inversion of phase takes place.

10. The method of preparing an aqueous dispersion of a copolymer of vinyl chloride and vinyl acetate which comprises mixing with said copolymer a plasticizer therefor, a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and dime'rized acid of soy bean oil, and also mixing with said copolymer a. soap, and adding water until an inversion of phase takes place.

11. A composition of matter containing dispersed particles of a mixture of synthetic resin selected drom the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, with a plasticizer therefor, and a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an allrylene glycol and a dimerized acid of a, vegetable drying oil, in an aqueous medium containing a hydrophilic colloidal dispersing agent selected from the group consisting of soaps, proteins, soiubilized casein and colloidal clay.

12. A composition or matter containing dispersed particles of a mixture of synthetic resin selectedfrom the group consisting of polyvinyl chloride, and copolymers 0! vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, with a plasticizer therefor, and a heat-reaction product, at a temperature in the range olbetween" about C. and 300 C., or a mix containing rosin, an alkanolamine, ethylene glycol and a dimerized acid of a vegetable drying oil, in an aqueous medium containing soap.

13. A composition oi matter containing dispersed particles of a mixture or synthetic resin selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, with a plasticizer therefor, and a heat-reaction product, at a. temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and dimerized acid oi. soy bean oil, in an aqueous medium containing a hydrophilic colloidal dispersing agent selected from the group consisting of soaps, proteins, solubllized casein and colloidal clay.

14. A composition of matter containing dispersed particles of a mixture of synthetic resin selected from the group consisting of polyvinyl chloride, and copolymers of vinyl chloride and vinyl acetate, and alkyl methacrylate polymers, with a plasticizer therefor, and a heatreaction product, at a temperature in the range of between about 180 C. and 300 C., 01' a mix containing rosin, an alkanolaminaan alkylene glycol and dimerized acid of soy beanoil, in an aqueous medium containing soap.

15. A composition of matter containing dispersed particles or a m xture of an alkyl methacrylate polymer with a plasticizer therefor, and a heat-reaction product, at a, temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and, dimerized acid or soy bean oil, in an aqueous medium containing a hydrophilic colloidal dispersing agent selected from the group,

consisting of soaps, proteins, solubllized casein and colloidal clay.

16. A composition of matter containing dispersed particles or a mixture of an alkylimethacrylate polymer with a plasticizer therefor, and a heat-reaction product. at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, an alkylene glycol and a dimerized acid of a vegetable drying oil, in an aqueous medium containing soap.

17. A composition of matter containing dispersed particles or a mixture of polyvinyl chloride with a plasticizer therefor, and a heat-reaction product, at a temperature in the range of between about 180 C. and 300 C., of a mix containing rosin, an alkanolamine, ethylene glycol and dimerized acid of soy been 011, in an aqueous medium containing a hydrophilic colloidal dispersing agent selected from the group consisting of soaps, proteins, solubilized casein and colloidal clay.

18. A composition of matter containing dispersed particles of a mixture of polyvinyl chloride with a-plasticizer therefor, and a heat-reaction persed particles of a. mixture'oi a copolymer of vinyl chloride and vinyl acetate with a plasticizer therefor and a heat-reaction product, at a temgnome 11 e perature'in the muse otbet'een about 180' O. and 300 C., o! omix tainingmmelkanol emine, ethylene a and dimerized acid of no! beanoilQmm ueouaigediumcontainin e hydr phy from the w ll consisting o1 loops, proteins, golubilized casein and colloidal c117.

20. A composition of matter oontninin: dieperaed particles 0! a mixture of a copolymer of dium containing loop.

12 vinyl chloride and-vinyl acetate with o pheticilutherefor and a heat-reaction product, st e temperature in the range of between about 180 C. and 300 (3., o! a. mix containing rosin, an 0.1-

dal dispersing scent selected 5 '-kanolamine, an alkylene glycol end a dimeriaed acid or a vegetable drying oil, inm aqueous me- CHAR-LE8 1". BROWN. 

